Reaction of nonconjugated olefinic compounds with alpha-beta-unsaturated carbonylic compounds



Patented Sept. 29, 19.42 I I s 2,297,039

"UNITED, STATES'PATENT OFFICE f REACTION OF NONCONJUGATED OLEFINIO COMPOUNDS WITH a-fi-UNSATURATED CARBONYLIC ()OMPOUNDS Johannes Andreas van Melsen, Amsterdam, Netherlands, assignor to Shell Development Company, San Francisco, Calii'., a corporation of Delaware 1 No Drawing. Application March 20, 1939, Serial No.-8 263,056. In the. Netherlands March 26,

14 Claims. (01. 260-537) The present invention relates to a process for products and not with the oleflnic compound per the production of ow-unsaturated carbonylic se to produce the monomeric. fi-v-unsaturated compounds containing the structural grouping addition product. By simply heating, for exam- III, by 3,4-addition' of non-conjugated olefinic ple, such easily polymerizable olefinic compounds compounds to unsaturated compounds containing as, for instance, styrene, methyl styrene, p-hyan ethylenic linkage in conjugatedrelation' to droxy styrene, vinyl acetate, vinyl chloride, vinyl one or more C=O groups, according to the genethyl ether, non-conjugated terpenes, and the eral equation: i like, to the reaction temperature together with i H v I H the above augends,highmolecular weight resinous products are obtained which contain, in general, II I only small amounts of the monomeric 3,4-addil H C tion product. on the other hand, when employ- 11 III ing more diflicultly polymerizable Olefinic com- (Addend) (augend) I (product) pounds, such as certain secondary mono-olefinic Since this reaction is not, strictly speaking, acon- 15 y a bons, according to U. S. Patent No. densation, alkenylation or a polymerization, it is 2,055,456, for ple, t e' p ons of the referred to hereingimply as reaction by 3,4- monomeric 3,4-addition product in the crude redditi fl action mixture are considerably higher and. may

An obje t, of t invention i t provide a under favorable circumstances even constitute method whereby olefines may be reacted with the main Product In all eases, however, eve

compounds containing the structure II by 3,4- en e p oying the less easily polymerizable addition with a minimum of loss due to polymeriolefimo mp s an appreciabl por n, if zation a th r id a ti n not the maJor portion, of the reaction product The above reaction, in its broader aspect. is consists of h molecular Weight polymeric genemuy applicable t t reaction f products and the yield of the desired 3,4 -addition jugated oleflnic compounds containing an isoproduct s respondingly 10W.

lated ethylenic linkage in which at least one hy- According to the present invention the desired drogen atom is attached to at least one of the 34'add1t10n re is made o p oceed at a unsaturated carbon t by 3,4.. t t much faster rate than the various polymerization saturated compounds containing an aliphatic reactions by executing the eact on in't e presethylenic linkage in conjugated relation to one or enee Of a Catalyst- The lesult, s a be easil) more 3:0 groups. (By an isolated ethylenic seen, is to materially increase the proportion of linkage is meant a single ethylenic linkage or an the desired 3,4-addition Product i lihe P o u t ethylenic linkage too far removed from any other 15 and se t e y eldunsaturated bond to be affected by conjugation.) I a e fou d. that the desired 3,4-addition re- However, since the various addends and augends, action y e S ctively cataly e y y one or containing the structures I and II respectively, a m ture of several materials. The most efiecall possess varying tendencies to polymerize, and li e catalysts that I have so far found are the since the above 3,4-addition reaction takes place, Ordinarily-Solid, Co o metals of atomic numin general, at an appreciable rate only at elevated hers greater than Forexample, iron, coppe temperatures, such as, for example, from 100 C. ba t, l; lead, tin, manga es chromium, t 250 i ,11 cases, upon mixing any particuthallium, vanadium, zinc, cadmium and bismuth lat addend with any particular augend and heatare suitable. I have furthermore fOllIld that ing to the reaction temperature, the reaction theee materials e, in eneral, equally efiective mixture consists of a mixture of products in proin the form of Various alloys- Thus, for a p portions roughly proportional to the relative excellent results may be obtained with various tendencies of the 3,4-addition reaction and the alloy steels, suc as t e va s grades o c e various polymerization reactions to take place. copper, chromium, and vanadium steels, and the Thus, for example, ifan easily polymerizable like. Even corrosion resistant alloys give excelolefinic compound is heated tothe reaction temlent results. Of these various metals, copper,

perature with an augend containing the structure iron and mixtures or alloys thereof with other II, the predominant reaction is polymerization metals appear to give the best results.

and such 3,4-addition as does take place takes Aside from the metals per se I may, in general, place predominantly by the addition of a polyalso employ the oxides and the various salts merized addencl to form high molecular weight thereof. Although the metal oxides and metalsalts do not, in general, afiord ashigh yields of the desired 3.4-addition product as the metals per se, they may, however, be advantageously employed in many cases. The metal salts, for example, although somewhat less effective than the metals may be advantageous in certain cases since they are, in general, effective in even very small amounts. Of the various metal salts those of neutral or basic reaction (i. e. non-acidic) are, in general, superior. One particularly effective group of metal salts are the salts of the abovementioned group of metals derived from carboxylic acids such as, for instance the acetates, fol-mates, isobutyrates, propionates, oxalates, and the like. 1

In order to insure the maximum catalytic activity, it is referable that the metal, if a metal be use'df-b n'a finely divided state. Thus, for

'example, see cuttings. fine lathe turnings, or

filings-maybe used. ,The best results, however, are obtainedriwith even more finely divided particles, such as copper powder, bronze powder, iron powder and the like.

By executing the reaction according to the present invention in the presence of the abovedescribed catalytic materials, substantial quantities of the monomeric 3,4-addition product may be obtained when employing even the more easily polymerizable non-conjugated olefinic compounds and much better yields of the desired product may be obtained when employing the less easily polymerizable olefinic compounds.

The reaction may, be carried into effect by mixing the addend and augend in any desired proportions in any suitable reaction vessel and heating at the desired temperature in the presence of an efiective amount of one or a mixture of the above-described catalysts. Although the process may be executed continuously, an intermittent or batch process is very suitable for moderate scale production. In such cases where the reactants have sufliciently high boiling points the reaction may be executed at atmospheric pressure in an open reaction vessel or a reaction vessel equipped with a suitable return condenser. Since, however, it is often desired to employ low boiling olefinic addends and to execute the reaction at a temperature above the boiling point of the reaction mixture, it is usually necessary to execute the reaction in a closed reaction vessel under the autogenic pressure (i. e., the pressure automatically generated by the reaction mixture in a closed vessel at the reaction temperature). For this purpose an autoclave equipped with heating means, and preferably also equipped with stirring and cooling means, is found to be quite suitable. While the addend and augent may be applied in any desired proportion, it is in general, advantageous, as regards the yield of the desired 3,4-addition product, to employ the least easily polymerizable reactant in substantial excess of the stoichiometric quantity. In many cases, how-ever, such as where one of the reactants is relatively costly or where certain economies in the recovery of the reaction product are possible, it may be more advantageous to employ approximately the. stoichiometric quantities or an excess of the more easily polymerizable reactant.

While the above catalysts may be advantageously employed in the preparation of monomeric 3.4-addition products using any non-conjugated olefine containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms, the results may vary considerably depending,

among other things, upon the character of the olefine,employed. Although the proportion of the desired 3,4-addition product in the reaction product is much higher when the reaction is executed in the presence of a catalyst, the proportion, and hence the yield, is still dependent, although to a lesser extent; upon the relative ease of polymerization of the reactants, chiefly the olefine.

As regards the relative ease of polymerization of the various applicable olefinic compounds, and hence the relative yields of 3,4-addition products obtainable therefrom, it should be noted that such non-conjugated olefinic compounds as, for example, vinyl chloride, vinyl acetate, methyl vinyl ether, and the like, in which the ethylem'c linkage is a terminal vinyl group to which a. negative substituent is directly attached, have, in general, a strong tendency to polymerize. In view of the lower yields obtainable when employing these easily' polymerizable materials, olefinic compounds containing this. structure are the least preferred. Furthermore, mono olefinic compounds such as the acyclic aliphatic mono-olefines (for example, propene, butene-2, pentene-Z, hexene-3, decene, hexydecenepropylene trimer, methyl allyl ether, allyl sulfide, allyl acetate, elaidic acid, oleic acid, allyl benzene, allyl cyclohexane, and the like) and alicyclic olefines (for example, cyclohexene, cyclopentene, 1-methyl cyclopentene-2 and the like) are, in general, preferred to olefines which contain a plurality of isolated or accumulated ethylenic linkages such as, for' instance, 1,4-cyclohexadiene, 1,5-hexadiene, ethyl cyclohexadiene, 2,6-dimethyl octadiene-2,6, dipentene, limonene, pinene, diprene, terpinolene, non-conjugated polyterpenes, allene and the like. Particularly suitable olefinic compounds to be used in the present process are those containing a branched carbon chain, as examples of which can be mentioned isobutylene,

trimethyl ethylene, di-isobutylene, tri-isobutylene and the like.

If desired, a high yield of a mixture of monomeric ISA-addition products may be produced by using a mixture of olefines. Such mixtures may be prepared very economically, for example, by utilizing the olefine content of various petroleum fractions. Cracked distillates and the various olefine extracts from petroleum processes, such as "Edeleanu extract, for example, are especially suitable. If it is desired that the mixture of monomeric 3,4-addition products be composed. of individual componds of closely related properties, an olefinic petroleum distillate boiling closely within the desired range should be chosen. It is often advantageous, especiallyj when employing cracked petroleum distillates, to subject the distillate to a mild refining treatment prior to the reaction. Mixtures of monomeric 3,4-addition products valuable for certain purposes may also be prepared, for example, by employing various fractions of isomeric mono-olefinic hydrocarbons such as may be obtained by polymerizing the lower olefines in a known manner with sulfuric acid, phosphoric acid catalysts, boron fluoride and the like, or by condensing a lower olefinic hydrocarbon. with a branched-chain paramne hydrocarbon.

The yields of the desired 3,4-addition product may also vary considerably depending uponthe polymerizing tendency and the reactivity of the augent. the aliphatic vii-unsaturated ketones, aldehydes, acids, acid chlorides, acid anhydrides, and

Applicable augends include in general esters of a-p-unsaturated acids in which the ethylenic linkage is of aliphatic character. In

general, the polymerizing tendency is materially less and the activity considerably greater in those augends in which the aliphatic ethylenic linkage is conjugated with respect to two C= groups. For these reasons augends of this type are, in general, preferred. As examples of these more preferable augends may be mentioned the a-fl-unsaturated dialdehydes, diketones, dicarboxylic acids, dicarboxylic acid chlorides, dicarboxylic acid anhydrides and monoand diesters of dicarboxylic acids. Of these available, twp-unsaturated dicarbonylic augends those of an acid nature such as maleic acid, fumaric acid, aconitic acid, itaconic acid, isopropylidene malonic acid, fumaramic acid, mesaconic acid, monochloro maleic acid, maleic sulfonic acid, dichloro fumaric acid, fumaryl chloride mesaconyl chloride, maleic chloride, maleic acid anhydride, citraconic acid anhydride, benzyl maleic acid anhydride, phenyl maleic acid anhydride, ethyl maleic acid anhydride, dichloro maleic acid anhydrlde and the like, give the most useful products and are preferred.

In view of the fact that maleic acid, maleic acid anhydride and fumaric acid are produced in large quantities through the oxidation of benzol and are readily available at a low cost, these augends, as far as the practical application of the process is concerned, are by far the most important.

Aside from the above described augends containing aliphatic ethylenic linkages in conjugated relation to one or more C=O linkages, there also exists a group of applicable compounds, such as maleic acid, which, although not included in the above definition, readily revert under the reaction conditions into compounds of the desired structure. Compounds behaving in this way, since they react as augends in the 3,4-addition reaction only after their self-conversion to the desired e-p-unsaturated structure, are considered in the present instance as full equivalents of the above described compounds.

The amount of catalyst preferably employed depends primarily upon the activity of the catalyst, which, if a metal is employed, is in turn dependent upon the state of subdivision. In general, the less finely divided the metal is, the larger is the quantity required to most effectively catalyze the reaction; Since it is found, however, that in general, the beneficial effect of the catalyst is roughly proportional to the amount present, and since an excess of catalyst is in no way harmful, fairly large quantities of the catalyst are preferably employed. Thus, for example, when employing metal lathe turnings, I often employ a quantity ranging from about 25-100% or higher of the combined weight of the reactants. When employing catalysts in a more finely divided state of subdivision, much smaller quantitles may be used with an equivalent effect. Metal salts, when employed, may be used in quantitles as low as, for instance 0.5% of the combined weights of the reactants.

In order to insure an even temperature throughout the reaction, and to provide an intimate contact with the catalyst (if a heterogeneous catalyst is used) it is preferable, but not essential, that the mixture be mildly agitated during the reaction. This may be especially advantageous when using finely divided metal powders since they otherwise often tend to settle as a cake on the bottom of the reaction vessel.

The temperature at which the present process is preferably executed depends somewhat upon the activity, heat stability and critical properties of the oleflnic addend, as also upon the character of the augend (for instance sometimes the I melting point and varies in general between about and 250 C. In many cases upon reaching the reaction temperature, the temperature of the reaction mixture may rise more or less suddenly due to the heat of the exothermic reaction. In such cases where the temperature increase due to this cause is very pronounced, it is preferable to maintain the reaction mixture within the preferred temperature range by discontinuing the heating, or if necessary by applying suitable cooling.

The reaction time may vary from a few minutes to several hours depending upon the particular reactants and temperatures employed. If desired, the reaction may be executed in the presence of inert solvents or diluents such as aromatic hydrocarbons, v aliphatic hydrocarbons. chlorinated paraflins, saturated ethers, saturated esters, and the like and/or in the presence of a third reactant such'as an alcohol, epoxide, amine or the like, capable of simultaneously reacting under the prevailing conditions with the augend by other than 3,4-addition.

The desired 3,4-addition product, or products. maybe recovered from the reaction mixture, in general, in any one of several ways. Thus, for example, if the reaction mixture, after being freed of the catalyst, is subjected to a suitable fractional distillation, the unconverted reactants are first recovered. Upon continuing the distillation, usually in vacuo, the desired 3,4-addition product is obtained, whilst the various polymeric products remain in the still as a residue. Other methods of recovery especially suitable for the particular product in question will be readily apparent.

According to the process of the present invention, by executing the reaction in the presence of the above described catalytic materials, the ratio of the desired 3,4-addition product to polymerization products in the crude reaction mixture is materially increased and much better yields are obtained. The advantageous results obtained when using the present catalysts are illustrated, for example, in the following table,

The 3,4-addition products which may be produced more economically and in materially better yields according to the process of the present invention, are p-v-unsaturated compounds containing the structural grouping III. As will be apparent from the general reaction, the olefinic addend attaches itself as a radical through one of its ethylenic carbon atoms and without loss of its ethylenic linkage to one ofthe unsaturated carbon atoms of the conjugated ethylenic group of the'augend, and a hydrogen atom from the ethylenic linkage of the addend attaches itself to the other unsaturated carbon atom of the conjugatcd ethylenic linkage of the augend, where by the conjugated ethylenic group of the augend disappears. Thus, when reacting an olefinic compound with, for example, maleic or fumaric acid, a compound of the structure wherein R represents a radical attached through an unsaturated carbon atom and derived from one of the above-described applicable addends by removal of an ethylenic hydrogen atom, is obtained. The present Sgt-addition, products are valuable compounds suitable for numerous applications such 'as,-for example, as addition agents for lubricants to improve the lubricating properties and to prevent corrosion of cylinder walls and other metal machine parts; in the permanent water-proofing of fabrics; as reactants in the production of alkyd-type and rezyl-type resins; in the preparation of special detergents, wetting agents, leather treating dopes and many other useful materials. Since, furthermore, the 3.4-addition products retain intact the original C=O group (or groups) of the augend, they may be further reacted according to the usual methods with various agents capable of reacting with carboxylic acids, carboxylic acid chlorids, ketones etc. to form the corresponding amines, amides, esters, ethers, alcohols, thiocyanates, alkali salts, etc.

Having described my invention in a detailed and comprehensive manner and having given specific examples illustrating the advantageous results obtainable thereby, I claim as my invention all that is commensurate with the scope of the appended claims, interpreted as broadly as possible in view of the prior art.

I claim as my invention.

1. A process for the production of valuable 3,4-addition products which comprises reacting a mono-olefinic' hydrocarbon with an unsaturated maleic acid, maleic acid anhydride and fumaric acid at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and non-acidic carboxylic acid salts thereof.

2. A process for the production of valuable 3,4- addition products which comprises reacting a mono-olefinic compound devoid of conjugation with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to two carboxyl groups at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically- .active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and nonacidic carboxylic acid salts thereof.

3. A process for the production of valuable 3,4- addition products which comprises reacting a mono-olefinic compound devoid of conjugation w th an unsaturated compound containingan aliphatic ethylenic linkage in conjugated relation to 'two C- O groups at a temperature between 100 C. and 250 C. in the presence of an efiective amount of a finely divided catalytically-activeand bismuth, and oxides and non-acidic carboxylic acid salts thereof.

4. A process for the production 0t valuable 3,4- addition products which comprises reacting a mono-olefinic compound devoid of conjugation with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a 0:0 group at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically-active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and non-acidic carboxylic acid salts thereof.

5. A process for the production of valuable 3,4- addition products which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to two C=O groups at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically-active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin,

manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and nonacidic carboxylic acid salts thereof.

6. A process for the production of valuable 3,4- addition products which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a 0:0 group at a temperature between C. and 250 C. in the presence of an effective amount of a finely divided catalytically-active carboxylic acid salt of an ordinarily-solid, common metal of the class consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth.

'7. A process for the production of valuable 3,4- addition products which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a C=0 group at a temperature between 100 C. and 250 C. in the presence of an efiective amount of finely divided cupreous metal.

8. A process for the production of valuable 3,4- addition products, which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in con jugated relation to a 0:0 group at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided ferrous metal.

9. A process for the production of valuable 3,4- addition products, which comprises reacting an olefim'c compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a (3:0 group at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically-active ordinarily-solid common metal of the class consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chromium, thallium, vanadium, zince, cadmium and bismuth.

10. A process for the production of valuable 3,4-addition products, which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a C= group at a temperature between 100 C. and 250 C. in the presence of an effective amount of a finely divided catalytically-active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin, manganese chromium thallium, vanadium, zinc, cadmium and bismuth, 'and oxides and nonacidic carboxylic acid salts thereof.

11. A process for the production of valuable 3,4-addition products, which comprises reacting a mono-olefinic hydrocarbon having a branched carbon chain with an unsaturated compound selected fromthe group consisting of maleic acid, maleic acid anhydride and fumaric acid at a temperature between 100 C. and 250 C. in the presence of an efiective amount of a finely divided catalytically-active material selected from the group consisting of iron, copper, cobalt, nickel. lead, tin manganese, chromium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and non-acidic carboxylic acid salts thereof.

12. A process for the production of valuable 3,4-addition products, which comprises reacting a mono-olefinic compound devoid of conjugation and containing a branched carbon chain with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a 0:0 group, at a temperature between C. and 250 C. in the presence of an efiective amount of a finely divided catalytically-active material selected from the group consisting of iron, copper, cobalt, nickel, lead, tin, manganese, chro mium, thallium, vanadium, zinc, cadmium and bismuth, and oxides and non-acidic carboxylic acid salts thereof.

13. A process for the production of valuable 3,4-addition products which comprises reacting an olefinic compound containing an isolated ethylenic linkage in which at least one hydrogen atom is attached to at least one of the unsaturated carbon atoms, with unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a 0:0 group, at a temperature between 100 C. and 250 C. in the presence of an effective amount of finely divided copper.

14. A process for the production of valuable 3,4-addition products which comprises reacting a mono-olefinic hydrocarbon having a branched carbon chain with an unsaturated compound containing an aliphatic ethylenic linkage in conjugated relation to a 0:0 group at a temperature between 100 C. and 250 C. in the presence of an effective amount of finely divided copper.

J OHANNES ANDREAS VAN MELSEN. 

